Catalyst preparation method

ABSTRACT

The method provides an eggshell catalyst in which the metal oxide is concentrated in an outer layer on the support.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/881,933 filed Jul. 15, 2013, which is a U.S. National Phaseapplication of PCT International Application No. PCT/GB2011/051889,filed Oct. 4, 2011, and claims priority of British Patent ApplicationNo. 1018152.7, filed Oct. 27, 2010, the disclosures of which areincorporated herein by reference in their entireties for all purposes.

BACKGROUND OF THE INVENTION

This invention relates to a method of preparing catalysts supported onmetal aluminate supports.

Metal aluminate-supported catalysts are used in a number of industrialprocesses, including methanation and steam reforming processes, such aspre-reforming, primary reforming and secondary reforming. In such casesthe catalytically-active metal is typically nickel, but other transitionmetals or precious metals, may also be used.

In methanation and steam reforming processes, pellets comprising nickeloxide on alumina or calcium aluminate are typically installed and thereduction of the nickel oxide to the active elemental nickel carried outin situ.

U.S. Pat. No. 4,707,351 describes steam-reforming catalysts made of alow-silica calcium aluminate cement composition in a saddleconfiguration. The catalysts were prepared by mixing calcium aluminatewith water and polyvinylacetate, stamping shapes from the resultingmaterial, drying and calcining the saddles at up to 1400° C. beforeimpregnation with nickel nitrate. The impregnated saddles were furtherdried and calcined to generate the catalyst precursor. In this process,the calcium aluminate support was hydrated during the shaping processand then calcined to increase its strength and define the micromimetricproperties prior to impregnation with nickel nitrate.

Heretofore it has been seen as necessary to impregnate supports toachieve a uniform dispersion of the nickel compound within the pelletssuch that upon calcination the metal oxide is uniformly dispersed withinthe pellet, thereby maximising the metal surface area and hence catalystactivity.

SUMMARY OF THE INVENTION

Applicants have found that by using aqueous solutions of nickel acetateat elevated temperatures, an egg-shell catalyst precursor may beproduced in which the metal oxide formed upon calcination isconcentrated as an outer surface layer on the metal aluminate supportand is not uniformly distributed. Moreover, the properties of suchcatalysts are enhanced in comparison to the known catalysts.

Accordingly, the invention provides a method for preparing a catalystcomprising the steps of:

-   -   (i) impregnating a calcined support comprising a metal aluminate        with a solution comprising nickel acetate at a temperature        40° C. and drying the impregnated support,    -   (ii) calcining the dried impregnated support, to form nickel        oxide on the surface of the support and    -   (iii) optionally repeating steps (i) and (ii) on the nickel        oxide coated support.

The invention further provides an eggshell catalyst obtainable by themethod.

The invention further provides a process for the steam reforming ofhydrocarbons comprising the step of contacting a mixture of hydrocarbonand steam at elevated temperature and pressure with the eggshellcatalyst.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an EPMA image of a cross-section of a cylindrical catalystpellet prepared according to the present invention depicting an eggshelllayer of nickel oxide.

DETAILED DESCRIPTION OF THE INVENTION

By the term “eggshell catalyst” we mean that the catalytically activemetal or metals are not uniformly distributed within the catalystsupport but are concentrated at the surface and therefore form a thinlayer, with the metal or metals being absent beneath this layer. Thethickness of the eggshell layer is preferably ≤1000 μm, more preferably≤800 μm, most preferably ≤300 μm. The thickness of the layer may readilybe established using electron probe microanalysis (EPMA) or opticalmicroscopy on cross-sectioned catalysts.

The catalyst support comprises a metal aluminate. The metal aluminatemay be a Group II aluminate such as magnesium aluminate or calciumaluminate, and/or may comprise a transition metal aluminate such asnickel aluminate. The support has been calcined, i.e. subjected to aheating step to alter its physiochemical properties. The calcinedsupport is impregnated with the solution of nickel acetate.

The catalyst support is preferably prepared from a calcium aluminatecement. By the term calcium aluminate cement we include those hydrauliccements containing one or more calcium aluminate compounds of theformula nCaO.mAl₂O₃ where n and m are integers. Example of such calciumaluminate compounds include calcium monoaluminate (CaO.Al₂O₃),tricalcium aluminate (3CaO.Al₂O₃), penta calcium trialuminate(5CaO.3Al₂O₃), tricalcium penta aluminate (3CaO..5Al₂O₃), and dodecacalcium hepta aluminate (12CaO.7Al₂O₃). Some calcium aluminate cements,e.g. the so-called “high alumina” cements, may contain alumina inadmixture with, dissolved in, or combined with, such calcium aluminatecompounds. For example, a well known commercial high alumina cement hasa composition corresponding to about 18% calcium oxide, 79% alumina and3% water and other oxides. This material has a calcium:aluminium atomicratio of about 1:5, i.e. 2CaO.5Al₂O₃. Calcium aluminates are oftencontaminated with iron compounds, but these are not believed to bedetrimental to the present invention. Suitable cements include thecommercially available Ciment Fondu, and Secar 50, Secar 71, Secar 80available from Kerneos and CA-25, CA-14, CA-270 available from Almatis.

The support composition employed in the present invention preferably hasa calcium:aluminium atomic ratio within the range 1:3 to 1:12, morepreferably 1:3 to 1:10, most preferably 1:4 to 1:8. Where the calciumaluminate cement is a “high alumina” cement, no additional alumina maybe necessary but, in general, the support is desirably made from acalcium aluminate cement to which an additional amount of alumina, whichmay be in the form of a transition alumina, monohydrate or trihydrate,has been added.

To accelerate setting, an amount of lime (CaO), e.g. up to 15% by weightof the composition, may also be incorporated into the supportcomposition.

Hence the support preferably comprises a refractory compositionconsisting of a calcined mixture of alumina, one or more of said calciumaluminate compounds and optionally lime.

Other oxidic materials, e.g. titania, zirconia or lanthana, may bepresent in the support composition. While silica may in some cases beincorporated, for use as a steam reforming support, a low silicacontent, i.e. less than 1% by weight, preferably less than 0.5% byweight, based on the weight of the oxidic material in the supportcomposition is desirable, as silica has an appreciable volatility understeam reforming conditions. The support composition preferably contains≤25% by weight, more preferably ≤15% by weight, most preferably ≤10% byweight of oxidic material other than alumina or metal aluminate.

The shaped catalyst support may be made by forming a calcium aluminatecement powder, optionally with additional alumina and/or lime, into thedesired shape, curing the cement and subsequently calcining the shapedsupport.

Processing aids, such as graphite and/or a metal stearate (e.g. Mg or Alstearate), may be incorporated into the composition prior to shaping.Typically the proportion of graphite is 1 to 5% by weight of thecomposition. The amounts of metal stearate included may be in the range0.1 to 2.0% by weight.

A typical composition suitable for pellet formation comprises 30 to 70%by weight of a calcium aluminate cement (comprising 65 to 85% by weightof alumina and 15 to 35% by weight of CaO) mixed with 24 to 48% byweight of alumina, 0 to 15% by weight of lime, and 2 to 5% by weight ofgraphite.

The composition is desirably shaped into pellets using known techniques,but may also be prepared as extrudates or granules. The length, widthand height of such shaped units may be in the range 3-50 mm. The supportmay be in the form of saddles as described in the aforesaid U.S. Pat.No. 4,707,351 but preferably the support is pressed into pellets in theform of cylinders, which may have one or more through holes, for exampleas described in WO 2004/014549. More preferably the shaped support is inthe form of a cylindrical pellet having between 1 and 12 holes extendingthere-through, especially 3-10 holes e.g. of circular cross section, andoptionally between 2 and 20 flutes or lobes running along the length ofthe pellet. Suitable diameters for such pellets are in the range 4-40 mmand the aspect ratio (length/diameter) is preferably ≤2. A particularlypreferred shape is a highly domed cylindrical pellet in the form of acylinder having a length C and diameter D, which has one or more holesextending therethrough, wherein the cylinder has domed ends of lengths Aand B, such that (A+B+C)/D is in the range 0.50 to 2.00, and (A+B)/C isin the range 0.40 to 5.00. Such shapes are described in WO 2010/029323A1 and WO 2010/029324 A1. C is preferably in the range 1 to 25 mm and Dis preferably in the range 4 to 40 mm.

After shaping, the cement in the shaped catalyst support should be curedand the support dried, typically at under 200° C., and then calcined.Curing of the calcium aluminate cement may take place before or during adrying step, e.g. by spraying or immersing the shaped catalyst supportwith water prior to drying or by heating the shaped catalyst supportunder conditions of controlled relative humidity prior to volatilisingresidual water. Calcination is typically carried out by heating theshaped units to between 400 and 1400° C. in air for between 1 and 16hours. The catalyst support strength increases, while the porosity andsurface area decrease, as the calcination temperature increases. Hencethe support calcination should be effected at sufficient temperature toobtain the required mechanical strength but should not be so high thatthe surface area and porosity are unduly reduced.

The shaped calcined catalyst support preferably has a total surfacearea, as measured by nitrogen absorption, of 0.5 to 40 m²g⁻¹,particularly 1 to 15 m²g⁻¹, and a pore volume of 0.1 to 0.3 cm³·g⁻¹, asdetermined by mercury porosimetry.

Prior to the final calcination, the support may be “alkalised” byimpregnation with a solution of an alkali such as potassium hydroxide.This serves to minimise lay down of carbon on the catalyst during steamreforming. Alkali oxide, e.g. potash, levels of up to about 5% wt on thecalcined support may be used.

The calcined catalyst support is then impregnated with a solutioncomprising nickel acetate [Ni(OOCCH₃)₂], which may be provided as ahydrated salt. Preferably all the nickel is provided as nickel acetate.The impregnation solution may comprise one or more additional metalcompounds, such as one or more transition metals, for example chromium,manganese cobalt, iron, copper or zinc, or lanthanides such as lanthanumor cerium.

Aqueous impregnation solutions are preferably used. Whereas organicsolvents such as methanol, ethanol or acetone may be used or included inthe aqueous solution, this is less preferred.

The concentration of nickel in the impregnating solution is desirably inthe range 0.5-1.0M.

Impregnation should be performed at a temperature ≥40° C., preferably≥50° C., more preferably ≥60° C., most preferably ≥70° C. A maximumtemperature below boiling is desired.

Impregnation may be performed at atmospheric or elevated pressure usingknown techniques, including immersion of the calcined catalyst supportin a nickel acetate solution or by so-called “incipient wetness”impregnation where the volume of solution used equates approximately tothe pore volume of the support material.

Following impregnation, the impregnated support is dried and calcined.The support drying is preferably performed at a temperature in the range25-250° C., more preferably in the range 50-150° C. at atmospheric orreduced pressure. Drying times may be in the range 1-24 hours. Thecalcination step to convert the impregnated nickel acetate into nickeloxide is preferably performed at a temperature in the range 250-850° C.The calcination may be performed in air or an inert gas such asnitrogen. The drying and calcination may be performed in a single step.An advantage of the present invention, by virtue of the use of nickelacetate, the lower metal content and the increased metal concentrationat the surface of the catalysts, is that the evolution of greenhousegases during calcination, is minimised and in particular the emission ofnitrogen oxides is eliminated, compared with current catalyst materials.

The catalytic metal content of the resulting catalyst may be determinedby a number of factors such as the metal content of the solution and theimpregnation conditions. Steam reforming catalysts formed byimpregnation typically have a NiO content in the range 10-35% wt.Precipitated pre-reforming catalysts can have NiO contents of 40-80% wtor more. Methanation catalysts typically have a NiO content in theregion of 30-35% wt. In the present invention, because the catalyticmetal oxide is concentrated at the surface of the support it is possibleto achieve improved catalyst activity with reduced metal loadings. Thishas clear commercial benefits. The catalytic metal oxide (NiO) contentof the calcined catalyst is preferably in the range 2 to 25% wt,preferably 4 to 15% wt. Whereas one impregnation may be sufficient togenerate the desired catalyst, preferably the impregnation, dryingand/or calcining steps are repeated until the catalytic metal oxidecontent of the calcined material is ≥2.5% wt, preferably ≥3% wt, morepreferably ≥4% wt. At these levels the concentration of Ni in theeggshell layer is preferably ≥10% wt.

The specific surface area of the catalytic metal (Ni) is suitably in therange 0.1 to 50 m²/g of catalyst. Within this range, larger areas arepreferred for reactions under 600° C.

One or more promoter compounds may be impregnated into the dried supportand/or the metal oxide coated support. Hence one or more promotercompounds may be included in the nickel acetate impregnating solution orthe promoter may be added subsequently by a separate impregnation. Thepromoter may be confined to the eggshell layer or may be distributedthroughout the catalyst support. Promoters include precious metals suchas platinum, palladium, iridium, ruthenium, rhodium and gold. Lanthanidemetals such as lanthanum and cerium may also be included as promoters.Water-soluble salts, particularly acetates, may be used as sources ofthe metal promoters. More than one promoter may be present andadditional alkali may also be added. The amount of promoter metal willtypically be in the range 0.1-5% wt on the calcined catalyst material.

The eggshell layer thickness of NiO in the catalyst is preferably in therange 0.15-1 mm for pellets with diameters ≥3 mm.

The catalysts may be used in oxidic or reduced form. Hence, the calcinedproduct may be provided in its oxidic form and reduction of the nickeloxide, to form elemental nickel carried out in situ, i.e. in the reactorin which the catalyst is to be used, with a hydrogen-containing gas.Known reduction techniques may be used.

Alternatively, the oxidic catalyst may be reduced ex situ and then theelemental metal coated with a thin passivating layer of oxide using anoxygen containing gas. In this way the catalyst may be transportedsafely to the user, and the reduction time to generate the activecatalyst and quantity of hydrogen used during the subsequent activation,reduced. This has clear benefits for the user. Therefore in oneembodiment, the method for preparing the catalyst further comprises thesteps of reducing the nickel oxide to elemental form with ahydrogen-containing gas mixture and subsequently passivating the surfaceof the elemental nickel with an oxygen-containing gas. Oxygen and carbondioxide gases may be used for example as described in U.S. Pat. No.4,090,980.

The eggshell catalysts prepared according to the invention may be usedin steam reforming processes such as primary steam reforming, secondaryreforming of a primary reformed gas mixture, and pre-reforming. Thecatalysts may also be used for methanation reactions, hydrogenationreactions and, in oxidic unreduced form, for the decomposition ofhypochlorite in aqueous solutions.

In steam reforming, a hydrocarbon, typically a methane-containing gassuch as natural gas or naphtha is reacted with steam and/or, whereappropriate, carbon dioxide, over a catalytically active material, oftencomprising nickel, to produce a gas containing hydrogen and carbonoxides. The hydrogen producing reactions are:CH₄+H₂O

CO+3H₂“CH₂”+H₂O→CO+2H₂

(“CH2” represents hydrocarbons higher than methane, for example normallygaseous hydrocarbons and normally liquid hydrocarbons boiling at up to200° C.). The analogous reactions with carbon dioxide can be carried outseparately or with the steam reaction.CH₄+CO₂→2CO+2H₂“CH₂”+CO₂→2CO+H₂

These reactions are strongly endothermic and the process is especiallysuitable when they are carried out with external heating as in tubularsteam reforming. Alternatively the heat can be supplied by heating thereactants and passing steam over the catalyst in an adiabatic bed or ina hybrid process in which oxygen is a reactant, so that heat evolved inoxidation is absorbed by the endothermic reactions. The hybrid processcan be applied to the product of the tubular or adiabatic process thatis, in “secondary reforming”, or to fresh feedstock (“catalytic partialoxidation” or “autothermal reforming”). Commonly these reactions areaccompanied by the water-gas shift reaction:CO+H₂O

CO₂+H₂

If the starting hydrocarbon is “CH₂” and the temperature is relativelylow, the methanation reaction (exothermic) may also occur.CO+3H₂→CH₄+H₂OCO₂+4H₂→CH₄+2H₂O

However, the steam reforming process is operated preferably in netendothermic conditions and the hydrogen containing gas produced containsat least 30% v/v of hydrogen on a dry basis. Preferably it contains lessthan 30, especially less than 10, % v/v of methane on a dry basis. Forthe production of hydrogen-containing synthesis gas, the outlettemperature is preferably at least 600° C. to ensure low methanecontent. While the temperature is generally in the range 750-900° C. formaking synthesis gas for ammonia or methanol production, it may be ashigh as 1100° C. for the production of metallurgical reducing gas, or aslow as 700° C. for the production of town gas. For the hybrid processusing oxygen, the temperature may be as high as 1300° C. in the hottestpart of the catalyst bed.

In pre-reforming, a hydrocarbon/steam mixture is subjected to a step ofadiabatic low temperature steam reforming. In such a process, thehydrocarbon/steam mixture is heated, typically to a temperature in therange 400-650° C., and then passed adiabatically through a fixed bed ofa suitable particulate catalyst, usually a catalyst having a high nickelcontent, for example above 40% by weight. The catalysts may be simplecylinders or a multi-holed, lobed shape. Pre-reforming catalysts aretypically provided in a pre-reduced and passivated form, although oxidiccatalyst may also be installed. During such an adiabatic low temperaturereforming step, any hydrocarbons higher than methane react with steam onthe catalyst surface to give a mixture of methane, carbon oxides andhydrogen. The use of such an adiabatic reforming step, commonly termedpre-reforming, is desirable to ensure that the feed to the steamreformer contains no hydrocarbons higher than methane and also containsa significant amount of hydrogen. This is desirable in order to minimisethe risk of carbon formation on the catalyst in the downstream steamreformer.

The pressure in steam reforming processes is typically in the range 1-50bar abs. but pressures up to 120 bar abs. are proposed. An excess ofsteam and/or carbon dioxide is normally used, especially in the range1.5 to 6, for example 2.5 to 5, moles of steam or carbon dioxide pergram atom of carbon in the starting hydrocarbon.

Where the catalyst is to be used for methanation, in order to remove lowconcentrations of CO and CO₂ (0.1-0.5% vol) from a hydrogen-containinggas, the hydrogen-containing gas is typically passed through aparticulate fixed bed of a nickel-containing catalyst at a temperaturein the range 230-450° C. and pressures up to about 50 bar abs or higherup to about 250 bar abs. Unlike steam reforming the catalyst arepreferably simple cylindrical pellets without through holes, althoughsuch pellets may be used if desired. Typical pellet diameters are in therange 2.5-6 mm, with lengths in the same range. The catalysts may beprovided in oxidic form or pre-reduced and passivated form.

EXAMPLES

The invention is further illustrated by reference to the followingExamples.

Example 1. Preparation of a Catalyst

Calcium aluminate cement was blended with alumina trihydrate and lime toobtain a mixture with a Ca:Al ratio of 10:43. Graphite (4 wt %) wasadded, and the resulting mixture pelleted using a hydraulic tablettingmachine to give cylinders of diameter 5.4 mm and length 5.4 mm. Thepellets were subjected to water-curing and calcination to obtain acalcined shaped support.

The pellets were impregnated with Ni acetate (Ni(O₂C₂H₃).4H₂O) with aconcentration of 0.851M for 20 minutes at 70° C. Following this, theNi-precursor was decomposed by calcining the impregnated supports at290° C. for 4 hrs in air. The impregnation and calcination were repeatedanother two times. The Ni content of the final catalyst was 4.37% byweight.

The resulting catalyst pellets had a clear surface enrichment of Ni (asNiO) on the surface of the support with no Ni in the centre of thepellet. The eggshell layer was about 0.75 mm thick as determined byelectron probe microanalysis (EPMA). EPMA was performed as follows; apolished sectional mount of the sample was made by resin mounting thepellet in epoxy resin, grinding and polishing, finishing with a silicapolish. The polished face was vacuum carbon coated. Measurements weretaken using a Jeol JXA-8500F electron probe microanalyzer with fivewavelength dispersive spectrometers and one SDD (silicon drift diode)EDX detector. A beam current of 200 nA was used with an acceleratingvoltage of 20 kV. Points were taken at every 8 μm for a time of 50 ms.The EPMA image is depicted in FIG. 1.

This experiment was repeated on the same calcium aluminate supportmaterial but formed into smaller cylindrical pellets (3.3 mm×3.3 mm)using a rotary tablet press. Eggshell enrichment of the surface of thepellets with NiO was observed with impregnation at 50° C. and at 70° C.The thickness of the eggshell layer as determined by optical microscopyon sectioned pellets was about 0.40 mm at 50° C. and about 0.20 mm at70° C. In both cases the centre of the pellets did not appear to containany NiO. When the experiment was repeated with impregnation at 20-25°C., no surface enrichment was observed and NiO was distributedthroughout the pellets.

The 3.3 mm×3.3 mm pellets impregnated at 70° C. had the following Nicontents.

Ni loading (% wt) Measured by XRF (at room temperature after the pelletsImpregnation had been heated to 700° C.) 1 2.3 2 4.3 3 5.3

The product of the 3^(rd) impregnation and calcination was termedcatalyst 1A.

Example 2 (Comparative Examples Using Ni Nitrate)

a) Ni nitrate impregnation at 50° C. The 3.3 mm×3.3 mm calcined calciumaluminate support pellets from Example 1 were impregnated with Ninitrate (Ni(NO₃)₂.4H₂O) at a concentration of 0.851M for 20 minutes 50°C. Following this, the Ni-precursor was decomposed by calcining theimpregnated supports at 290° C. for 4 hrs in air. Unlike thecorresponding experiment with Ni acetate, no eggshell enrichment of thesurface of the pellet with NiO was observed and NiO was distributedthroughout the pellet.

b) Ni nitrate impregnation at 70° C. The 3.3 mm×3.3 mm calcined calciumaluminate support pellets from Example 1 were impregnated with Ninitrate (Ni(NO₃)₂.4H₂O) at a concentration of 3.41M for 5 minutes at 70°C. The impregnated pellets were then removed and allowed to drain for 10minutes and dried at 110° C. for 6 hours. The dried impregnated pelletswere then heated at 100° C./hour to 650° C. and then held at 650° C. for6 hours to convert the nickel nitrate to nickel oxide. The impregnating,drying and calcining procedure was repeated on the nickel oxidecontaining pellets a further two times. The NiO content of this materialafter the final calcination was about 16.5 wt %. No eggshell surfaceenrichment at the surface of the pellets was observed and the NiO wasdistributed throughout the pellets. This comparative material was termedcatalyst 2A.

Example 3. Testing

The catalysts 1A and 2A were tested in a laboratory-scale steam reformerwith a reformer tube internal diameter of 1-inch. The catalysts werediluted with fused alumina chips (sieve fraction 3.35 mm-4.74 mm) andreduced using 50 vol % H₂ in N₂ at 600° C. for 2 hours. After catalystreduction, catalyst performance was assessed at a temperature of 750° C.The feed gas was natural gas mixed with steam at a steam:carbon ratio of3.0:1. The exit gas composition was analysed by gas chromatography.After 40 h at normal process conditions, catalyst 1A had a performance(ethane conversion) greater than 2A (64.07% conversion versus 63.20%conversion). Thus the catalyst of the present invention offers enhancedactivity than the conventional catalyst prepared from Ni nitrate,despite its considerably lower Ni content.

What is claimed:
 1. A catalyst comprising nickel or nickel oxide impregnated into a metal aluminate support in the form of a shaped pellet, extrudate, or granule, the form having a length, width and height in a range of from 3 to 50 mm, wherein the nickel or nickel oxide is present only in an eggshell layer, the eggshell layer including a surface of the support and having a thickness in a range of from 150 microns to 1000 microns.
 2. The catalyst according to claim 1 wherein the metal aluminate is selected from the group consisting of calcium aluminate, magnesium aluminate and nickel aluminate.
 3. The catalyst according to claim 1 wherein the metal aluminate is calcium aluminate and the calcined support is formed by shaping a calcium aluminate cement powder into a shaped support, curing the cement, and subsequently calcining the shaped support.
 4. The catalyst according to claim 3 wherein the support is alkalised by impregnation with a solution of an alkali.
 5. The catalyst according to claim 1 wherein the support is in the form of a cylindrical pellet having between 1 and 12 holes extending therethough.
 6. The catalyst according to claim 1 wherein the nickel is present as nickel (II) oxide.
 7. The catalyst according to claim 1 having a nickel oxide content in a range of from 2 to 25% wt.
 8. The catalyst according to claim 1 wherein one or more promoter compounds are impregnated into the support.
 9. The catalyst according to claim 1 wherein the metal aluminate is calcium aluminate and the support is formed by: shaping a mixture of calcium aluminate cement powder and one or both of alumina and lime into a shaped support, curing the shaped support, and subsequently calcining the shaped support.
 10. The catalyst according to claim 1 obtained by a method comprising the steps of: (i) impregnating a calcined support comprising a metal aluminate with a solution comprising nickel acetate at a temperature ≥40° C. to form an impregnated support and drying the impregnated support to form a dried impregnated support, and (ii) calcining the dried impregnated support, to form a nickel oxide coated support.
 11. The catalyst according to claim 10, wherein the method further comprises repeating steps (i) and (ii) on the nickel oxide coated support.
 12. The catalyst according to claim 10, wherein the method further comprises reducing the nickel oxide on the nickel oxide coated support with a hydrogen-containing gas mixture.
 13. The catalyst according to claim 1 wherein the support is in the form of a cylindrical pellet having a diameter of 4 to 40 mm and an aspect ratio ≤2.
 14. The catalyst according to claim 1 wherein the support is in the form of a domed cylindrical pellet having a cylindrical section having a length C and diameter D and domed ends of lengths A and B, such that (A+B+C)/D is 0.50 to 2.00 and (A+B)/C is 0.40 to 5.00.
 15. The catalyst according to claim 1 having a total surface area in a range of from 0.5 to 40 m²g⁻¹.
 16. The catalyst according to claim 1 having a pore volume in a range of from 0.1 to 0.3 cm³g⁻¹.
 17. The catalyst according to claim 3 wherein the support has a calcium:aluminium atomic ratio in a range of from 1:3 to 1:12.
 18. The catalyst according to claim 1 wherein the support has a silica content less than 1% by weight, based on the weight of the support composition.
 19. The catalyst according to claim 1 wherein the nickel is present as nickel metal. 